MoSi2 powders were fabricated respectively by mechanical alloying technique and sintering at different temperatures to prepare materials with different relative densities. The relative oxidation behavior of all MoSi2 materials at 1473K was investigated by TGA, SEM and XRD. The results show that the pesting is not found in all materials after being oxidized for 480h. The density has no essential relation to the pesting. The oxidation curve of specimens with lower density shows two-step oxidation kinetics. Both the first stage (0-1h) and the second stage (1-480h) nearly obey linear kinetics, but the oxidation rates are obviously different. The oxidation kinetics of MoSi2 with higher relative density nearly follows parabolic law. The mass gains of MoSi2 with the lowest relative density (78.6%) and the highest relative density (94.8%) are increased by 10.390 and 0.135 mg/cm2, respectively. The oxide scale of materials with lower densities is non-protective and makes the oxygen diffusion easy. A dense scale in the material with higher density is formed, which acts as a diffusion barrier to the oxygen atoms to penetrate into the matrix, showing much better high temperature oxidation resistance. The phases distribution of oxidation scale from the outside to the inside is SiO2→Mo5Si3→MoSi2.